CN106749413A - Using the preparation method of the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy - Google Patents
Using the preparation method of the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy Download PDFInfo
- Publication number
- CN106749413A CN106749413A CN201611045125.1A CN201611045125A CN106749413A CN 106749413 A CN106749413 A CN 106749413A CN 201611045125 A CN201611045125 A CN 201611045125A CN 106749413 A CN106749413 A CN 106749413A
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- flame retardant
- nitrogen containing
- epoxy
- reactive flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000004593 Epoxy Substances 0.000 title claims abstract description 33
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000005864 Sulphur Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims abstract description 13
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 229950003476 aminothiazole Drugs 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical class C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims description 5
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 abstract description 29
- 229920000647 polyepoxide Polymers 0.000 abstract description 29
- 238000001723 curing Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract description 5
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- -1 phospho Chemical class 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 238000002485 combustion reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 238000007711 solidification Methods 0.000 description 10
- 230000008023 solidification Effects 0.000 description 10
- 238000013007 heat curing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy.Preparation method is as follows：Parahydroxyben-zaldehyde, aminothiazole and solvent are sequentially added in the reactor equipped with condenser pipe and agitator, inert gas is passed through, first set reaction is carried out；The oxide of 9,10 dihydro, 9 oxa-, 10 phospho hetero phenanthrene 10 is added, the second secondary response is carried out, after reaction terminates, by system suction filtration, washing, drying be white or beige phosphorus-nitrogen containing reaction of Salmon-Saxl type fire retardant.The present invention has advantages below：1st, synthesis technique of the present invention is simple, cycle is short, and post processing is easy, it is easy to control and industrialized production.2nd, the fire retardant for preparing contains three kinds of ignition-proof elements of nitrogen phosphorus sulphur simultaneously, with cooperative flame retardant effect, can significantly improve the fire resistance of epoxy resin.3rd, prepared fire retardant is reactive flame retardant, while epoxy curing compound flame retardant effect is improved, can effectively keep its heat endurance and mechanical performance.
Description
Technical field
The present invention relates to a kind of preparation method of reactive flame retardant, and in particular to one kind application is phosphorous in the epoxy
The preparation method of nitrogen reaction of Salmon-Saxl type fire retardant.
Background technology
Epoxy resin as a kind of typical thermosetting polymer, with excellent cementability, mechanical property, electrical insulating property
And corrosion resistance, and shrinkage factor it is low, machine-shaping is easy, it is with low cost the advantages of, in integrated circuit, communications and transportation, aviation
The high-technology fields such as space flight aspect has obtained application widely.But epoxy resin belongs to combustible material, and in burning
When HRR it is big, calorific value is high, flame propagation speed, is difficult to extinguish, and also produces thick smoke sometimes and toxic gas, causes right
The harm of environment, the security of the lives and property to people constitutes huge threat.Therefore, improve epoxy resin fire resistance into
It is a big focus of research material performance instantly.
At present, ethoxyline resin antiflaming most common method mainly has two kinds of additive flame retardant and reaction-type flame-retarding.Addition type
Fire retardant refer to that fire retardant is added into epoxy resin, it will not react with epoxy resin, but disperse for physically
In epoxy resin.Although simple to operate but use problem along with some, such as with the poor compatibility of macromolecule matrix, cause base
Mechanical properties decrease of body etc..Reactive flame retardant is then that fire-retardant group is introduced in macromolecular material by chemical method, with
Improve anti-flammability, flame resistance and the suppression material combustion of composite.This method epoxy resin can not only be carried out it is fire-retardant,
The mechanical performance of epoxy resin can also preferably be kept.
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), as phenanthrene compound containing phospha, is new
Fire-retardant intermediate.Can be used for synthesizing the new small molecule of different functional groups using its active P-H key, phospho hetero phenanthrene structure is drawn
Enter and obtain good flame-retarding characteristic in different fire retardant or polymer.Contain N, P and S tri- simultaneously the invention discloses a kind of
The novel reaction type fire retardant of ignition-proof element is planted, and is added in epoxy resin, effectively raise epoxide resin material
Fire resistance and mechanical property.
The content of the invention
It is applied in epoxy resin while the three kinds of reactions of element of Nitrogen-and Phosphorus-containing sulphur object of the present invention is to provide a kind of
The preparation method of type fire retardant.
For realize technical scheme that the purpose of the present invention uses for：
1st, it is of the present invention for epoxy resin simultaneously three kinds of chemical structural formulas of the reactive flame retardant of element of phosphorus-nitrogen containing sulphur
For：
2nd, it is of the present invention for epoxy resin simultaneously three kinds of reactive flame retardants of element of phosphorus-nitrogen containing sulphur preparation method it is as follows：
Parahydroxyben-zaldehyde, aminothiazole and solvent are sequentially added in the reactor equipped with condenser pipe and agitator, is passed through lazy
Property gas, carry out first set reaction at 46~52 DEG C, after reaction 1.8~2.4 hours, add the miscellaneous -10- phosphorus of 9,10- dihydro-9-oxies
Miscellaneous phenanthrene -10- oxides (DOPO), continue to react 24~26 hours, after reaction terminates, system suction filtration, washing, drying is white
Color or beige phosphorus-nitrogen containing reaction of Salmon-Saxl type fire retardant.
Wherein, the aminothiazole described in above method is any one in thiazolamine or 2- aminobenzothiazoles.
The mol ratio of DOPO described in above method and aminothiazole is 1:1~1.2.
The mol ratio of DOPO described in above method and parahydroxyben-zaldehyde is 1:1~1.2.
Described inert gas is nitrogen.Solvent described in above method is ethanol, acetone, toluene, dichloromethane, dioxy six
One kind in ring etc..
Three kinds of reactive flame retardants of element of Nitrogen-and Phosphorus-containing sulphur, are applied to epoxy resin while being prepared by above method
In, hence it is evident that improve the fire resistance of epoxy resin cured product.When the phosphorus content of epoxy resin cured product reach 0.50wt%~
During 0.94wt%, vertical combustion grade can be by UL-94V-0 grades, and limited oxygen index is up to 33.3%.
The present invention compared with prior art, with advantages below：1st, the present invention prepares three kinds of Nitrogen-and Phosphorus-containing sulphur using one kettle way
The reactive flame retardant of element, synthesis technique is simple, cycle is short, and post processing is easy, it is easy to control and industrialized production.
2nd, fire retardant prepared by the present invention contains three kinds of ignition-proof elements of nitrogen phosphorus sulphur simultaneously, with cooperative flame retardant effect, low
Under addition, you can significantly improve the fire resistance of epoxy resin.
3rd, prepared Nitrogen-and Phosphorus-containing sulphur fire retardant is reactive flame retardant, is improving the same of epoxy curing compound flame retardant effect
When, can effectively keep its heat endurance and mechanical performance.
Specific embodiment
The reactive flame retardant of three kinds of elements of phosphorus-nitrogen containing sulphur of the present invention is specifically retouched below by embodiment
State.
Embodiment 1
In the container equipped with condenser pipe and agitator, sequentially added in the state of stirring 13.42g parahydroxyben-zaldehydes,
16.5g 2- aminobenzothiazoles and 200ml ethanol, are passed through nitrogen, after being reacted 2 hours at 50 DEG C, add 23.76g DOPO, after
Continuous reaction 24 hours.After reaction terminates, 3 times, drying white product 9,10- dihydros -9- are washed by system suction filtration, with ethanol
Oxa- -10- phospho hetero phenanthrenes -10- (4- hydroxyphenyls) (2- imino groups benzothiazole) methane -10- oxides (D-P-ABZ), yield
89%.
Embodiment 2
In the container equipped with condenser pipe and agitator, sequentially added in the state of stirring 16.10g parahydroxyben-zaldehydes,
19.8g 2- aminobenzothiazoles and 120ml acetone, are passed through nitrogen, after being reacted 1.8 hours at 52 DEG C, add 23.76g DOPO,
Continue to react 26 hours.After completion of the reaction, by solution suction filtration, with acetone 3~4 times, drying white product 9,10- bis- are washed
Hydrogen -9- oxa- -10- phospho hetero phenanthrenes -10- (4- hydroxyphenyls) (2- imino groups benzothiazole) methane -10- oxides (D-P-ABZ), produces
Rate 78%.
Embodiment 3
In the container equipped with condenser pipe and agitator, sequentially added in the state of stirring 14.76g parahydroxyben-zaldehydes,
18.15g 2- aminobenzothiazoles and 250ml acetone, are passed through nitrogen, after being reacted 2.2 hours at 48 DEG C, add 23.76g
DOPO, continues to react 26 hours.After reaction terminates, 3 times, drying white product 9,10- are washed by system suction filtration, with acetone
Miscellaneous -10- phospho hetero phenanthrenes-the 10- of dihydro-9-oxy (4- hydroxyphenyls) (2- imino groups benzothiazole) methane -10- oxides (D-P-ABZ),
Yield 70%.
The Measurement results of the fire retardant D-P-ABZ that the present embodiment is prepared are as follows：
1H NMR (400MHz, DMSO-d6), δ (ppm)：9.54,9.51 (s, 1H), 8.98-9.10 (m, 1H), 8.14-8.21
(m, 2H), 7.44-7.78 (m, 4H), 7.13-7.41 (m, 6H), 6.96-7.08 (m, 2H), 6.69-6.74 (m, 2H), 5.57-
5.85(m,1H)；
31P-NMR (162MHz, DMSO-d6), δ (ppm):28.59,29.96；
HRMS(EI+)：calcd.for C26H20N2O3PS[M+H]+471.0932, found 471.0896；
FTIR (KBr, cm-1), 3410.9 (Ph-OH), 3217.5 (N-H), 3036.0 (Ar-H), 2961,2920 (C-H),
1447.3 (P-Ph), 1381.8 (P-C), 1224.1 (P=O), 1117.0 (P-O-Ar).
Its structural formula is：
Embodiment 4
In the container equipped with condenser pipe and agitator, 13.42g parahydroxyben-zaldehydes, 11g are sequentially added in the state of stirring
Thiazolamine and 200ml ethanol, are passed through nitrogen, after being reacted 2.4 hours at 50 DEG C, add 23.76g DOPO, continue to react 26
Hour.After reaction terminates, 4 times, drying light brown product 9 are washed by system suction filtration, with ethanol, 10- dihydro-9-oxies are miscellaneous-
10- phospho hetero phenanthrenes -10- (4- hydroxyphenyls) (2- imino thiazoles) methane -10- oxides (D-P-AZ), yield 85%.
Embodiment 5
Sequentially added in the container equipped with condenser pipe and agitator 16.10g parahydroxyben-zaldehydes, 13.2g thiazolamines and
120ml acetone, is passed through nitrogen, after being reacted 1.8 hours at 50 DEG C, adds 23.76g DOPO, continues to react 25 hours.React
Bi Hou, washs 3 times, drying light brown product 9 by solution suction filtration, with acetone, and the miscellaneous -10- phospho hetero phenanthrenes of 10- dihydro-9-oxies -
10- (4- hydroxyphenyls) (2- imino thiazoles) methane -10- oxides (D-P-AZ), yield 70%.
Embodiment 6
In the container equipped with condenser pipe and agitator, sequentially added in the state of stirring 14.76g parahydroxyben-zaldehydes,
12.1g thiazolamines and 250ml acetone, are passed through nitrogen, after being reacted 2 hours at 50 DEG C, add 23.76gDOPO, continue anti-
Answer 24 hours.Reaction terminate after, wash by system suction filtration, with acetone 4 times, drying both obtain light brown product 9,10- dihydro-9-oxies
Miscellaneous -10- phospho hetero phenanthrenes -10- (4- hydroxyphenyls) (2- imino thiazoles) methane -10- oxides (D-P-AZ), yield 63%.
The Measurement results of fire retardant D-P-AZ are as follows：
1H NMR (400MHz, DMSO-d6), δ (ppm):9.50,9.46(s,1H)；8.47-8.64(m,1H)；8.16-8.22
(m,2H)；7.70-7.79(m,2H)；7.30-7.59(m,3H)；7.15,7.10 (dd, J=8.4Hz, 1.6Hz, 2H)；7.03
(dd, J=8.0Hz, 0.8Hz, 1H)；6.76-6.88 (d, J=3.6Hz, H)；6.66-6.72(mm,2H)；6.51,6.58(d,J
=3.6Hz, 1H)；5.70,5.41 (dd, J=14Hz, 10Hz, 1H)；
31P-NMR (162MHz, DMSO-d6), δ (ppm):28.85,30.18；
HRMS(EI+)：calcd.for C22H18N2O3PS[M+H]+421.0776,found 421.0764；
FTIR (KBr, cm-1), 3396.0 (Ph-OH), 3238.3 (N-H), 3065.8 (C=C-H), 3012.2 (Ar-H),
(C-H), 29261.7,2917.0 1444.6 (P-Ph), 1375.9 (P-C), 1233.1 (P=O), 1111.1 (P-O-Ar).
Its structural formula is：
It is of the invention by above example in order to investigate the flame retardant effect of the phosphorus-nitrogen containing reaction of Salmon-Saxl type fire retardant of present invention preparation
Phosphorus-nitrogen containing reaction of Salmon-Saxl type the fire retardant D-P-ABZ and D-P-AZ of preparation are respectively used to co-curing epoxy resin, and to solidification after
Testing of materials limited oxygen index and vertical combustion grade.
Application examples 1
The phosphorus-nitrogen containing sulphur fire retardant D-P-ABZ and 100g epoxy resin of any preparation of 6.32g above-described embodiments 1~3 are weighed in 140
DEG C stir and evenly mix；After 0.5 hour, 90 DEG C are cooled to, add 20.44g DDM to continue to stir, after obtaining uniform solution, by solution
Be transferred in preheated mould by 120 DEG C two hours, 150 DEG C 3 hours, 180 DEG C carry out heat cure in 1 hour；After solidification terminates
It is slowly cooled to room temperature, obtains flame retardant epoxy solidfied material.And vertical combustion and oxygen index (OI) test are carried out to gained epoxy curing compound, survey
Test result is as shown in table 1.
Application examples 2
The phosphorus-nitrogen containing sulphur fire retardant D-P-ABZ and 100g epoxy resin of any preparations of 1-3 of 9.73g above-described embodiments are weighed in 140
DEG C stir and evenly mix；After 0.5 hour, 90 DEG C are cooled to, add 19.74g DDM to continue to stir, after obtaining uniform solution, by solution
Be transferred in preheated mould by 120 DEG C 2 hours, 150 DEG C 3 hours, 180 DEG C carry out heat cure in 1 hour；Solidification is delayed after terminating
Slow cool down obtains flame retardant epoxy solidfied material to room temperature.And vertical combustion and oxygen index (OI) test, test are carried out to gained epoxy curing compound
Result is as shown in table 1.
Application examples 3
The phosphorus-nitrogen containing sulphur fire retardant D-P-ABZ and 100g epoxy resin of any preparations of 1-3 of 13.33g above-described embodiments are weighed in 140
DEG C stir and evenly mix；After 0.5 hour, 90 DEG C are cooled to, add 18.96g DDM to continue to stir, after obtaining uniform solution, by solution
Be transferred in preheated mould by 120 DEG C 2 hours, 150 DEG C 3 hours, 180 DEG C carry out heat cure in 1 hour；Solidification is delayed after terminating
Slow cool down obtains flame retardant epoxy solidfied material to room temperature.And vertical combustion and oxygen index (OI) test, test are carried out to gained epoxy curing compound
Result is as shown in table 1.
Application examples 4
The phosphorus-nitrogen containing sulphur fire retardant D-P-ABZ and 100g epoxy resin of any preparations of 1-3 of 17.14g above-described embodiments are weighed in 140
DEG C stir and evenly mix；After 0.5 hour, 90 DEG C are cooled to, add 18.17g DDM to continue to stir, after obtaining uniform solution, by solution
Be transferred in preheated mould by 120 DEG C 2 hours, 150 DEG C 3 hours, 180 DEG C carry out heat cure in 1 hour；Solidification is delayed after terminating
Slow cool down obtains flame retardant epoxy solidfied material to room temperature.And vertical combustion and oxygen index (OI) test, test are carried out to gained epoxy curing compound
Result is as shown in table 1.
Application examples 5
The phosphorus-nitrogen containing sulphur fire retardant D-P-AZ and 100g epoxy resin of any preparations of 4-6 of 6.32g above-described embodiments are weighed in 140 DEG C
Stir and evenly mix；After 0.5 hour, 90 DEG C are cooled to, add 20.29g DDM to continue to stir, after obtaining uniform solution, solution turned
Move in preheated mould by 120 DEG C 2 hours, 150 DEG C 3 hours, 180 DEG C carry out heat cure in 1 hour；Solidification is slow after terminating
Room temperature is cooled to, flame retardant epoxy solidfied material is obtained.And vertical combustion and oxygen index (OI) test, test knot are carried out to gained epoxy curing compound
Fruit is as shown in table 1.
Application examples 6
The phosphorus-nitrogen containing sulphur fire retardant D-P-AZ and 100g epoxy resin of any preparations of 4-6 of 9.73g above-described embodiments are weighed in 140 DEG C
Stir and evenly mix；After 0.5 hour, 90 DEG C are cooled to, add 19.48g DDM to continue to stir, after obtaining uniform solution, solution turned
Move in preheated mould by 120 DEG C 2 hours, 150 DEG C 3 hours, 180 DEG C carry out heat cure in 1 hour；Solidification is slow after terminating
Room temperature is cooled to, flame retardant epoxy solidfied material is obtained.And vertical combustion and oxygen index (OI) test, test knot are carried out to gained epoxy curing compound
Fruit is as shown in table 1.
Application examples 7
The phosphorus-nitrogen containing sulphur fire retardant D-P-AZ and 100g epoxy resin of any preparations of 4-6 of 13.33g above-described embodiments are weighed in 140
DEG C stir and evenly mix；After 0.5 hour, 90 DEG C are cooled to, add 18.64g DDM to continue to stir, after obtaining uniform solution, by solution
Be transferred in preheated mould by 120 DEG C DEG C two hours, 150 DEG C 3 hours, 180 DEG C carry out heat cure in 1 hour；Solidification terminates
After be slowly cooled to room temperature, obtain flame retardant epoxy solidfied material.And gained epoxy curing compound is carried out vertical combustion and oxygen index (OI) test,
Test result is as shown in table 1.
Application examples 8
The phosphorus-nitrogen containing sulphur fire retardant D-P-AZ and 100g epoxy resin of any preparations of 4-6 of 17.14g above-described embodiments are weighed in 140
DEG C stir and evenly mix；After 0.5 hour, 90 DEG C are cooled to, add 17.74g DDM to continue to stir, after obtaining uniform solution, by solution
Be transferred in preheated mould by 120 DEG C 2 hours, 150 DEG C 3 hours, 180 DEG C carry out heat cure in 1 hour；Solidification is delayed after terminating
Slow cool down obtains flame retardant epoxy solidfied material to room temperature.And vertical combustion and oxygen index (OI) test, test are carried out to gained epoxy curing compound
Result is as shown in table 1.
Comparative example 1
Weigh 100g epoxy resin to be stirred and evenly mixed in 90 DEG C, add 25g DDM to continue to stir, after obtaining uniform solution, be transferred to
120 DEG C are pressed in preheated mould 2 hours, 150 DEG C carry out heat cure in 3 hours；Solidification is slowly cooled to room temperature after terminating, and must hinder
Combustion epoxy curing compound.And vertical combustion and oxygen index (OI) test are carried out to gained epoxy curing compound, test result is as shown in table 1.
The phosphorus-nitrogen containing sulphur fire retarding epoxide resin of table 1 solidifies composition formula and its fire resistance
The above, preferred application example only of the invention, therefore can not according to this limit the scope of present invention application, i.e., successively
Equivalence changes and modification that the scope of the claims of the present invention and description are done, all should still belong in the range of the present invention covers.
Claims (9)
1. a kind of reactive flame retardant for applying phosphorus-nitrogen containing sulphur in the epoxy, with formula：
2. a kind of preparation method for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy, it is characterised in that described system
Preparation Method is as follows：Parahydroxyben-zaldehyde, aminothiazole and solvent are sequentially added in the reactor equipped with condenser pipe and agitator,
Inert gas is passed through, first set reaction is carried out；9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, is carried out
Secondary response is white by system suction filtration, washing, drying or beige phosphorus-nitrogen containing reaction of Salmon-Saxl type is fire-retardant after reaction terminates
Agent.
3. a kind of preparation side for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy according to claim 2
Method, it is characterised in that described first set reaction, reaction temperature is 46~52 DEG C, 1.8~2.4 hours reaction time.
4. a kind of preparation side for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy according to claim 2
Method, it is characterised in that the second described secondary response, 24~26 hours reaction time.
5. a kind of preparation side for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy according to claim 2
Method, it is characterised in that described aminothiazole is any one in thiazolamine or 2- aminobenzothiazoles.
6. a kind of preparation side for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy according to claim 2
Method, it is characterised in that the mol ratio of the DOPO and aminothiazole is 1:1~1.2.
7. a kind of preparation side for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy according to claim 2
Method, it is characterised in that the mol ratio of the DOPO and parahydroxyben-zaldehyde is 1:1~1.2.
8. a kind of preparation side for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy according to claim 2
Method, it is characterised in that described inert gas is nitrogen.
9. a kind of preparation side for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy according to claim 2
Method, it is characterised in that described solvent is the one kind in ethanol, acetone, toluene, dichloromethane, dioxane etc..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611045125.1A CN106749413B (en) | 2016-11-24 | 2016-11-24 | A kind of preparation method for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611045125.1A CN106749413B (en) | 2016-11-24 | 2016-11-24 | A kind of preparation method for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106749413A true CN106749413A (en) | 2017-05-31 |
| CN106749413B CN106749413B (en) | 2018-06-12 |
Family
ID=58974148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611045125.1A Active CN106749413B (en) | 2016-11-24 | 2016-11-24 | A kind of preparation method for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106749413B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467574A (en) * | 2018-11-13 | 2019-03-15 | 岭南师范学院 | It is a kind of novel based on vanillic aldehyde reactive flame retardant and its preparation, application |
| CN109485916A (en) * | 2018-11-20 | 2019-03-19 | 武汉工程大学 | A kind of synthesis and application of Aminopyrazine based flame retardant |
| CN110128474A (en) * | 2019-05-05 | 2019-08-16 | 三峡大学 | The preparation method and applications of the double DOPO thiazolium compounds of nitrogen phosphorus sulphur synergistic flame retardant |
| CN111253437A (en) * | 2020-03-10 | 2020-06-09 | 福建师范大学泉港石化研究院 | P/N/Si-containing multi-element reactive epoxy resin flame retardant and preparation method thereof |
| CN111732607A (en) * | 2020-06-29 | 2020-10-02 | 武汉理工大学 | Carboxylic acid compound containing phosphorus, nitrogen and boron, preparation method thereof, and preparation method and application of flame-retardant epoxy resin |
| CN113861510A (en) * | 2021-10-09 | 2021-12-31 | 常州大学 | Phosphorus-nitrogen-sulfur-containing flame retardant and preparation method and application method thereof |
| CN114605782A (en) * | 2022-03-23 | 2022-06-10 | 广西民族大学 | DOPO-based sym-triazine bridged thiazole flame-retardant epoxy resin and preparation method thereof |
| CN115612176A (en) * | 2022-10-21 | 2023-01-17 | 浙江工业大学 | Reactive flame retardant containing DOPO group and nitrogen-containing heterocycle and preparation method and application thereof |
| DE102023000325B3 (en) | 2023-02-03 | 2024-02-22 | lnstitut für Kunststofftechnologie und -recycling e.V. | Thiazole compounds as flame retardants containing phosphorus, nitrogen and sulfur and their use |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585456A (en) * | 2012-01-16 | 2012-07-18 | 苏州科技学院 | Halogen-free flame retardant composition for polyesters and application method thereof |
| CN106009040A (en) * | 2016-06-24 | 2016-10-12 | 福建师范大学 | Flame retardant containing phosphorus, nitrogen and sulfur and used for epoxy resin and preparation method of flame retardant |
-
2016
- 2016-11-24 CN CN201611045125.1A patent/CN106749413B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585456A (en) * | 2012-01-16 | 2012-07-18 | 苏州科技学院 | Halogen-free flame retardant composition for polyesters and application method thereof |
| CN106009040A (en) * | 2016-06-24 | 2016-10-12 | 福建师范大学 | Flame retardant containing phosphorus, nitrogen and sulfur and used for epoxy resin and preparation method of flame retardant |
Non-Patent Citations (3)
| Title |
|---|
| YAJUN CHEN ET AL.: "The Flame Retardant Group-Synergistic-Effect of a Phosphaphenanthrene and Triazine Double-Group Compound in Epoxy Resin", 《J. APPL. POLYM. SCI.》 * |
| YING ZHAO ET AL.: "Synthesis of maleimido-substituted aromatic s-triazine and its application inflame-retarded epoxy resins", 《POLYMER DEGRADATION AND STABILITY》 * |
| 班大明: "新型翰林阻燃剂的合成、表征及性能研究", 《材料导报 B：研究篇》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467574B (en) * | 2018-11-13 | 2021-03-16 | 岭南师范学院 | Reactive flame retardant based on vanillin as well as preparation and application thereof |
| CN109467574A (en) * | 2018-11-13 | 2019-03-15 | 岭南师范学院 | It is a kind of novel based on vanillic aldehyde reactive flame retardant and its preparation, application |
| CN109485916A (en) * | 2018-11-20 | 2019-03-19 | 武汉工程大学 | A kind of synthesis and application of Aminopyrazine based flame retardant |
| CN110128474A (en) * | 2019-05-05 | 2019-08-16 | 三峡大学 | The preparation method and applications of the double DOPO thiazolium compounds of nitrogen phosphorus sulphur synergistic flame retardant |
| CN110128474B (en) * | 2019-05-05 | 2021-10-19 | 三峡大学 | Preparation method and application of nitrogen-phosphorus-sulfur ternary synergistic flame retardant bis-DOPO thiazole compound |
| CN111253437A (en) * | 2020-03-10 | 2020-06-09 | 福建师范大学泉港石化研究院 | P/N/Si-containing multi-element reactive epoxy resin flame retardant and preparation method thereof |
| CN111732607A (en) * | 2020-06-29 | 2020-10-02 | 武汉理工大学 | Carboxylic acid compound containing phosphorus, nitrogen and boron, preparation method thereof, and preparation method and application of flame-retardant epoxy resin |
| CN111732607B (en) * | 2020-06-29 | 2023-07-18 | 武汉理工大学 | Carboxylic acid compound containing phosphorus, nitrogen and boron, preparation method thereof and preparation method and application of flame-retardant epoxy resin |
| CN113861510A (en) * | 2021-10-09 | 2021-12-31 | 常州大学 | Phosphorus-nitrogen-sulfur-containing flame retardant and preparation method and application method thereof |
| CN113861510B (en) * | 2021-10-09 | 2023-02-28 | 常州大学 | Phosphorus-nitrogen-sulfur-containing flame retardant and preparation method and application method thereof |
| CN114605782A (en) * | 2022-03-23 | 2022-06-10 | 广西民族大学 | DOPO-based sym-triazine bridged thiazole flame-retardant epoxy resin and preparation method thereof |
| CN115612176A (en) * | 2022-10-21 | 2023-01-17 | 浙江工业大学 | Reactive flame retardant containing DOPO group and nitrogen-containing heterocycle and preparation method and application thereof |
| DE102023000325B3 (en) | 2023-02-03 | 2024-02-22 | lnstitut für Kunststofftechnologie und -recycling e.V. | Thiazole compounds as flame retardants containing phosphorus, nitrogen and sulfur and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106749413B (en) | 2018-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106749413A (en) | Using the preparation method of the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy | |
| CN106009040B (en) | It is a kind of for phosphorus-nitrogen containing sulphur fire retardant of epoxy resin and preparation method thereof | |
| CN108440598B (en) | Preparation method and application of sulfur-nitrogen-phosphorus composite flame retardant | |
| CN102838778A (en) | Preparation method of nitrogen and phosphorus fire retardant, nitrogen and phosphorus fire retardant and application thereof | |
| CN110157041A (en) | It is a kind of containing double DOPO bases and the reactive flame retardant of nitrogen and its preparation method and application | |
| CN100473655C (en) | Method for preparing no-halogen fire-proof phosphorus-containing compound | |
| CN102617645B (en) | 1-oxo-4-hydroxymethyl-1-phospholane-2, 6, 7-trioxabicyclo [2, 2, 2] octane derivative with flame retardation effect and preparation of derivative | |
| CN102718802B (en) | Aryloxy substituted tripolyphosphazene epoxide and preparation method and application thereof | |
| CN103044708A (en) | High-efficiency N/P flame retardant, as well as preparation method and application thereof | |
| CN110183727B (en) | Benzothiazole nitrogen phosphorus sulfur ternary synergistic flame retardant containing double DOPO units, and preparation method and application thereof | |
| CN104558683A (en) | DOPO-containing cyclic phosphate flame retardant as well as preparation method and application thereof | |
| CN105175735A (en) | Branched phosphorus-nitrogen type flame retardant and preparation method therefor | |
| CN113248634B (en) | Chitosan-Schiff/DOPO flame retardant, preparation method thereof and modified epoxy resin | |
| CN109021287A (en) | A kind of phosphorus nitrogen sulfur type fire retardant and its application in the epoxy | |
| CN105295300A (en) | DOPO derivative flame retardant as well as preparation and application of DOPO derivative flame retardant | |
| CN104231309A (en) | Oxaphosphaphenanthrene flame retardant, preparation method and application thereof | |
| Liu et al. | Impact of a novel phosphorus-nitrogen flame retardant curing agent on the properties of epoxy resin | |
| CN103012847A (en) | Efficient nitrogen and phosphorus fire retardant for epoxy resin and preparation method of efficient nitrogen and phosphorus fire retardant | |
| CN112142954A (en) | Modified epoxy resin and preparation method thereof | |
| CN110387042A (en) | Epoxy resin the type fire retardant of topology convergence containing DOPO and preparation method | |
| CN108586807A (en) | A kind of flame retarding function graphite alkene and its preparation and application | |
| CN110128702A (en) | Benzene sulphones nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO, preparation method and applications | |
| CN110156840A (en) | A kind of Phosphorus-nitrogen flame retardant and preparation method thereof containing DOPO | |
| CN108084228B (en) | It is a kind of to contain nitrogen, the compound of three kinds of ignition-proof elements of phosphorus and bromine, preparation method and application | |
| CN110467747A (en) | The fire-retardant complex compound of metal ion and preparation method with schiff bases structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |